CN102515619B - Polyether amine modified polycarboxylic water reducer and preparation method thereof - Google Patents
Polyether amine modified polycarboxylic water reducer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyether amine modified polycarboxylic water reducer and a preparation method thereof. The water reducer is a polyether amine modified polycarboxylic acid copolymer which has the weight-average molecular weight of 5,000 to 120,000 and is obtained by performing amidation on polycarboxylic acid copolymer which has the weight-average molecular weight of 1,000 to 30,000 and comprises 5.0 to 50.00 weight percent of carboxylic structural unit I and a carboxylic structural unit II, and a polyether amine monomer A at the temperature of between 80 and 200 DEG C; the preparation method comprises the following steps of: copolymerizing itaconic acid, and unsaturated carboxylic monomer B under the action of an initiator in a solution at the temperature of between 50 and 100 DEG C to obtain a polycarboxylic copolymer with the molecular weight of between 1,000 and 3,000; and performing amidation on the copolymer and the polyether amine monomer A at the temperature of between 80 and 200 DEG C. The polyether amine modified polycarboxylic water reducer is high in concrete water-reducing rate under the condition of low accretion, and keeps good concrete slump simultaneously.
Description
Technical field
The invention belongs to technical field of concrete additives, relate to mortar or the reinforcement of concrete superplasticizer, specifically a kind of novel poly carboxylic acid series water reducer and preparation method thereof.
Background technology
High performance water reducing agent of polyocarboxy acid is called as third generation Concrete superplastizer, has that volume is low, water-reducing rate is high, the Molecular Structure Design degree of freedom is large, advantages of environment protection, becomes study hotspot and the development priority in 21st century concrete admixture field.
A kind of formula and manufacture method thereof of polycarboxylic acid super-plasticizer are disclosed in patent CN101205127A, at first make the esterification under the condition that catalyzer and stopper exist of poly glycol monomethyl ether and maleic anhydride generate large monomer, then make with allyl polyglycol, vinylformic acid, methylpropene sodium sulfonate the polycarboxylic acid super-plasticizer that copolymerization under the condition of initiator obtains Xu Fangxing at ammonium persulphate.But, because the polymerization activity of allyl polyglycol, poly glycol monomethyl ether maleic acid ester is not enough, can remain in a large number in the polycarboxylic acid super-plasticizer that synthesize, cause the water-reducing rate of gained superplasticizer low, slump retention deficiency.
Patent CN102101906A discloses the preparation method of a kind of acid amides/imide-type high density polycarboxylate high performance water-reducing agent.This patent is first unsaturated acid anhydride and monobasic hydramine acylation reaction to be obtained acylate by the first step; second step is that pol yalkylene glycol monoalkyl ether, unsaturated acid (acid anhydride) are carried out catalytic esterification; obtain esterification products; the 3rd the step be with acylate, esterification products, sulphonic acids minor comonomer under the effect of initiator and copolymerization conditioning agent; carry out free-radical polymerizedly then copolymerization product pH value being adjusted into 6-7, the poly carboxylic acid series water reducer of system.Water-reducing rate and the slump retaining of this water reducer are better; the water reducer that can prepare high density (70-80%) reduces transportation cost; but use unsaturated acid anhydride and monobasic hydramine to carry out acylation reaction; very difficult assurance does not have the generation of esterification; and preparation process is comparatively complicated, and technique controlling difficulty is larger.
Patent CN102181020A discloses the method for the synthetic high performance water reducing agent of polyocarboxy acid of amidation reactive monomer copolyreaction.This patent is (methyl) Acrylic Acid Monomer and an end to be contained amino methoxy polyoxyethylene base ether prepare a kind of polymerisable monomer by amidate action under catalyst action, then with (methyl) Acrylic Acid Monomer, chain shift monomer under the initiator effect in the aqueous solution after copolymerization with in basic solution and the poly carboxylic acid series water reducer of system.In this water reducer molecular structure, main side chain connects by amido linkage, and water-reducing property is excellent, but it is harsh to prepare polymerisable monomer process conditional at amidate action, is difficult to control.
Summary of the invention
The purpose of this invention is to provide a kind of high concrete water-reducing ratio that still has under the low-dosage condition, have simultaneously polyether amine modified polycarboxylic water reducer of good concrete slump maintenance and preparation method thereof.
Polyether amine modified polycarboxylic water reducer of the present invention, it is that to carry out by co-poly carboxylic acid and polyetheramine monomer weight-average molecular weight that amidation obtains under 80 ℃～200 ℃ be 5000～120000 polyethex amine modification co-poly carboxylic acid; Described co-poly carboxylic acid contains 5.0%～50.0% weight, and following carboxylic acid group's structural units I and the following weight-average molecular weight that is derived from carboxylic acid group's structural unit II of being derived from is 1000～30000 carboxylic acid polyalcohol, wherein:
Structural units I is
Wherein: M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
The structural unit II is
Wherein: R
1Expression hydrogen, methyl or COOM group, R
2Expression hydrogen or methyl group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
Described polyetheramine monomer A is represented by general formula (3)
Wherein: R
3Identical or different, expression hydrogen, methyl or ethyl; R
4Alkyl or its mixture of expression hydrogen or 1-18 carbon atom; N represents the adduct number of oxyalkylene group, is the Arbitrary Digit in 1-300.
A kind of method for preparing described polyether amine modified polycarboxylic water reducer, it comprises following two steps:
Step 1: in the aqueous solution of 50 ℃～100 ℃, be 1000～30000 co-poly carboxylic acid with accounting for the methylene-succinic acid of unsaturated monomer gross weight 5.0%～50.0% or itaconic anhydride or itaconate and carry out copolymerization by the unsaturated carboxylic acid monomer B of general formula (4) expression under the condition that initiator exists, obtaining molecular weight; Wherein: unsaturated carboxylic acid monomer B is
Wherein: R
5Expression hydrogen, methyl or COOM group, R
6Expression hydrogen or methyl group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group; Work as R
5During expression COOM group, there is or forms acid anhydrides with the COOM form between two COOM groups of monomers B;
Step 2: the step 1 co-poly carboxylic acid that obtains and the polyetheramine monomer A that is represented by general formula (3) are carried out amidate action at 80 ℃～200 ℃, obtain polyether amine modified polycarboxylic water reducer of the present invention; Wherein:
In the weight of polyetheramine monomer A and step 1, the ratio of unsaturated monomer gross weight is 1.5:1～10:1.
Described initiator is one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide, tertbutyl peroxide.
Described initiator amount is 0.2%～10.0% of total monomer weight.
The polyether amine modified polycarboxylic water reducer weight-average molecular weight is 5000～120000.Molecular weight is too low or too high, and the performance of high performance water reducing agent of polyocarboxy acid is all deteriorated.U.S. Waters 1515 HPLC SYSTEM high performance liquid chromatographs are adopted in the test of weight-average molecular weight, configuration Ultrahydrogel
TMWater-soluable gel post, Waters 2414 differential refraction detectors are with 0.1mol/L NaNO
3The aqueous solution is moving phase, measures take polyoxyethylene glycol as standard substance.
There is no special restriction to being used for polyetheramine monomer A of the present invention, as long as it is can be by the monomer of above general formula (3) expression.
There is no special restriction to being used for unsaturated carboxylic acid monomer B of the present invention, as long as it is can be by the monomer of above general formula (4) expression.Monomers B comprises: vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid and butenoic acid, and univalent metal salt, divalent metal salt, ammonium salt and organic amine salt.Monomers B is a kind of or its mixture wherein.
When the preparation co-poly carboxylic acid, can also add following monomer component:
Unsaturated polyether comprises vinyl polyether, allyl polyether, methacrylic polyethers, 3-methyl-3-butenyl polyethers;
(methyl) acrylate, comprise methyl acrylate, ethyl propenoate, butyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, dimethylaminoethyl acrylate, vinylformic acid diethylin ethyl ester, the polyalkylene glycol acrylate ester, polyalkylene glycol acrylate polypropylene glycol ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, dimethylaminoethyl methacrylate, methacrylic acid diethylin ethyl ester, the methacrylic acid polyethylene glycol, methacrylic acid polyethylene glycol polypropylene glycol ester,
Unsaturated sulfonic acid or its salt comprise sodium allyl sulfonate, methallylsulfonic acid sodium, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic or its salt, vinylformic acid sulphur ethyl ester, methacrylic acid sulphur ethyl ester;
Unsaturated amides comprises acrylamide, Methacrylamide, n-methylolacrylamide, N,N-DMAA;
Vinyl ester comprises vinyl acetate, propionate, tertiary ethylene carbonate;
Fumarate or maleic acid ester comprise monomethyl fumarate, monomethyl ester, fumaric acid list propyl ester, fumaric acid mono—n—butylester, fumaric acid mono methoxy polyethylene glycol ester, fumaric acid mono methoxy polyethylene glycol polypropylene glycol ester, monomethyl maleate, ethyl maleate, toxilic acid list propyl ester, butyl maleate, toxilic acid mono methoxy polyethylene glycol ester, toxilic acid mono methoxy polyethylene glycol polypropylene glycol ester.
When implementing amidate action, can or vacuumize to make amidate action more complete by nitrogen gas stream, airflow, Reaction time shorten, raise the efficiency simultaneously.
After amidate action is completed, select as required the solid content of conditioned reaction product or select not regulate.When not regulating the solid content of reaction product, can be by high performance water reducing agent of polyocarboxy acid cooling, that pulverizing prepares powder.
After amidate action is completed, select as required to regulate the pH value of product or select not regulate.If select to regulate the pH value, neutralization reagent used is sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia or organic amine or their aqueous solution.
In addition, polyether amine modified polycarboxylic water reducer of the present invention can be used from mortar or concrete with known cement water reducing agent, setting accelerator, hardening accelerator, retardant, air entrapment agent, defoamer, tackifier, economization agent one.Polyether amine modified polycarboxylic water reducer of the present invention still has high concrete water-reducing ratio under the low-dosage condition, have simultaneously good concrete slump and keep.
Embodiment
The present invention is further described by following examples, but the present invention is not produced any restriction.
Listed abbreviation below having used in an embodiment:
A-1: the polyetheramine monomer, structural formula is
, wherein the addition mode of oxyethane and propylene oxide is random copolymerization
A-2: the polyetheramine monomer, structural formula is
, wherein the addition mode of oxyethane and propylene oxide is random copolymerization
A-3: the polyetheramine monomer, structural formula is
B-1: vinylformic acid
B-2: maleic anhydride
B-3: methacrylic acid
C-1: methoxy poly (ethylene glycol) (n=9) acrylate
C-2: acrylamide
Embodiment 1
Add 100.0g B-2,50.0g methylene-succinic acid and 780.0g water in the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, stir and be warming up to 80 ℃.Drip respectively simultaneously 200.0g ammonium persulfate aqueous solution (be dissolved in 180.0g water by the 20.0g ammonium persulphate and obtain), 20.0g 3-thiohydracrylic acid and 850.0g B-1, time for adding is controlled at respectively 180 minutes, 150 minutes and 150 minutes, temperature of reaction is controlled at 78～82 ℃.After dripping end, insulation under 78～82 ℃ about 60 minutes, make polyreaction complete, obtain co-poly carboxylic acid, be designated as PC-1, it is 3800 that GPC tests its weight-average molecular weight.
Add 200.0g co-poly carboxylic acid PC-1 and 957.95g A-1 in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 180 ℃ and be incubated 3h, the water in reaction system is reclaimed by condenser and with receiving trap.Then be cooled to 60 ℃ of left and right, add 130.0g 30%NaOH to regulate the pH value to 7.0 of product, and add 1460.0g water to regulate the solid content to 40% of product, obtain polyether amine modified polycarboxylic water reducer of the present invention, be designated as NPC-1, weight-average molecular weight is 48200.
Embodiment 2
Add 200.0g methylene-succinic acid and 775.0g water in the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, stir and be warming up to 95 ℃.Drip respectively simultaneously 200.0g ammonium persulfate aqueous solution (be dissolved in 180.0g water by the 20.0g ammonium persulphate and obtain), 25.0g 3-thiohydracrylic acid and 850.0g B-3, time for adding is controlled at respectively 210 minutes, 180 minutes and 180 minutes, temperature of reaction is controlled at 78～82 ℃.After dripping end, insulation under 78～82 ℃ about 60 minutes, make polyreaction complete, obtain co-poly carboxylic acid, be designated as PC-2, it is 3100 that GPC tests its weight-average molecular weight.
Add 200.0g co-poly carboxylic acid PC-2 and 517.5g A-2 in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 120 ℃ and be incubated 1h, the water in reaction system is reclaimed by condenser and with receiving trap; Then keep approximately 120 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, the time is 2h approximately.Then be cooled to 60 ℃ of left and right, add 95.0g 30%NaOH to regulate the pH value to 7.0 of product, and add 835.0g water to regulate the solid content to 40% of product, obtain polyether amine modified polycarboxylic water reducer of the present invention, be designated as NPC-2, weight-average molecular weight is 23100.
Embodiment 3
Add 400.0g methylene-succinic acid and 780.0g water in the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, stir and be warming up to 52 ℃.Drip respectively simultaneously 200.0g sodium persulfate aqueous solution (be dissolved in 180.0g water by the 20.0g Sodium Persulfate and obtain), 20.0g 3-thiohydracrylic acid and 600.0g B-1, time for adding is controlled at respectively 210 minutes, 180 minutes and 180 minutes, temperature of reaction is controlled at 50～54 ℃.After dripping end, insulation under 50～54 ℃ about 60 minutes, make polyreaction complete, obtain co-poly carboxylic acid, be designated as PC-3, it is 3400 that GPC tests its weight-average molecular weight.
Add 200.0g co-poly carboxylic acid PC-3 and 544.9g A-3 in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 120 ℃ and be incubated 1h, the water in reaction system is reclaimed by condenser and with receiving trap; Then keep approximately 120 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in reaction system is progressively risen to-0.05MPa, keep this vacuum tightness until react completely, the time is 2h approximately.Then be cooled to 60 ℃ of left and right, add 150.0g 30%NaOH to regulate the pH value to 7.0 of product, and add 820.0g water to regulate the solid content to 40% of product, obtain polyether amine modified polycarboxylic water reducer of the present invention, be designated as NPC-3, weight-average molecular weight is 26400.
Embodiment 4
Add 200.0g methylene-succinic acid and 370.0g water in the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, stir and be warming up to 80 ℃.Drip respectively simultaneously 200.0g sodium persulfate aqueous solution (be dissolved in 180.0g water by the 20.0g Sodium Persulfate and obtain), 30.0g 3-thiohydracrylic acid and the 1200.0g Acrylic Acid Monomer aqueous solution (be dissolved in 400.0g water by 400.0g B-1,400.0g C-1 and obtain), time for adding is controlled at respectively 180 minutes, 150 minutes and 150 minutes, temperature of reaction is controlled at 78～82 ℃.After dripping end, insulation under 78～82 ℃ about 60 minutes, make polyreaction complete, obtain co-poly carboxylic acid, be designated as PC-4, it is 7600 that GPC tests its weight-average molecular weight.
Add 200.0g co-poly carboxylic acid PC-4,136.9g A-1 and 131.5g A-3 in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 120 ℃ and be incubated 1h, the water in reaction system is reclaimed by condenser and with receiving trap; Then keep approximately 120 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, the time is 2h approximately.Then be cooled to 60 ℃ of left and right, add 90.0g 30%NaOH to regulate the pH value to 7.0 of product, and add 470.0g water to regulate the solid content to 40% of product, obtain polyether amine modified polycarboxylic water reducer of the present invention, be designated as NPC-4, weight-average molecular weight is 33600.
Embodiment 5
Add 100.0g methylene-succinic acid and 420.0g water in the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, stir and be warming up to 80 ℃.Drip respectively simultaneously 150.0g sodium persulfate aqueous solution (be dissolved in 135.0g water by the 15.0g ammonium persulphate and obtain), 20.0g Thiovanic acid and the 1300.0g Acrylic Acid Monomer aqueous solution (be dissolved in 400.0g water by 700.0g B-1,200.0g C-2 and obtain), time for adding is controlled at respectively 180 minutes, 150 minutes and 150 minutes, temperature of reaction is controlled at 78～82 ℃.After dripping end, insulation under 78～82 ℃ about 60 minutes, make polyreaction complete, obtain co-poly carboxylic acid, be designated as PC-5, it is 4200 that GPC tests its weight-average molecular weight.
Add 200.0g co-poly carboxylic acid PC-5,273.7g A-1 and 144.9g A-2 in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 120 ℃ and be incubated 1h, the water in reaction system is reclaimed by condenser and with receiving trap; Then keep approximately 120 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, the time is 2h approximately.Then be cooled to 60 ℃ of left and right, add 110.0g 30%NaOH to regulate the pH value to 7.0 of product, and add 670.0g water to regulate the solid content to 40% of product, obtain polyether amine modified polycarboxylic water reducer of the present invention, be designated as NPC-5, weight-average molecular weight is 26200.
Application examples
According to high-performance water reducing agent test request in GB8076-2008 " concrete admixture " standard, adopting the reference cement of Beijing Xingfa Cement Co., Ltd's production, the river sand of silt content 0.8% fineness modulus 2.6, nominal particle diameter 5mm～10mm and the 10mm～20mm continuous grading rubble of silt content 0.2% is material, concrete mix according to table 1 regulation has been tested the indexs such as water-reducing rate, air content, slump hold facility, and test result sees Table 2.
Table 1 test concrete mix
| Starting material | Cement | River sand | The 5-10mm stone | The 10-20mm stone |
| Proportioning, Kg/m 3 | 360 | 805 | 410 | 615 |
Table 2 high performance water reducing agent of polyocarboxy acid the performance test results
Annotate :/expression concrete does not have divergence
Test result from table 2, polyether amine modified polycarboxylic water reducer of the present invention still has high concrete water-reducing ratio under the low-dosage condition, still have concrete slump and degree of mobilization preferably after being mixed with simultaneously a hour of high performance water reducing agent of polyocarboxy acid of the present invention.
Claims (4)
1. polyether amine modified polycarboxylic water reducer is characterized in that this water reducer is that to carry out by co-poly carboxylic acid and polyetheramine monomer weight-average molecular weight that amidation obtains under 80 ℃～200 ℃ be 5000～120000 polyethex amine modification co-poly carboxylic acid; Described co-poly carboxylic acid contains 5.0%～50.0% weight, and following carboxylic acid group's structural units I and the following weight-average molecular weight that is derived from carboxylic acid group's structural unit II of being derived from is 1000～30000 polymers of carboxylic acid, wherein:
Structural units I is
Wherein: M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
The structural unit II is
Wherein: R
1Expression hydrogen, methyl or COOM group, R
2Expression hydrogen or methyl group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
Described polyetheramine monomer A is represented by following general formula (3)
Wherein: R
3Identical or different, expression hydrogen, methyl or ethyl; R
4The alkyl of expression hydrogen or 1～18 carbon atom; N represents the adduct number of oxyalkylene group, is the Arbitrary Digit in 1～300.
2. a method for preparing the described polyether amine modified polycarboxylic water reducer of claim 1, is characterized in that it comprises the steps:
Step 1: in the aqueous solution of 50 ℃～100 ℃, be 1000～30000 co-poly carboxylic acid with accounting for the methylene-succinic acid of total monomer weight 5.0%～50.0% or itaconic anhydride or itaconate and carry out copolymerization by the unsaturated carboxylic acid monomer B of following general formula (4) expression under the condition that initiator exists, obtaining molecular weight; Wherein: unsaturated carboxylic acid monomer B is
Wherein: R
5Expression hydrogen, methyl or COOM group, R
6Expression hydrogen or methyl group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group; Work as R
5During expression COOM group, there is or forms acid anhydrides with the COOM form between two COOM groups of monomers B;
Step 2: the step 1 co-poly carboxylic acid that obtains and the polyetheramine monomer A that is represented by general formula (3) are carried out amidate action at 80 ℃～200 ℃, obtain polyether amine modified polycarboxylic water reducer; Wherein:
In the weight of polyetheramine monomer A and step 1, the ratio of unsaturated monomer gross weight is 1.5: 1～10: 1.
3. the method for preparing polyether amine modified polycarboxylic water reducer according to claim 2, is characterized in that described initiator is one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide, tertbutyl peroxide.
4. the according to claim 2 or 3 described methods that prepare polyether amine modified polycarboxylic water reducer, is characterized in that described initiator amount is 0.2%～10.0% of total monomer weight.
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| CN107151294B (en) * | 2017-06-08 | 2020-03-24 | 中建材中岩科技有限公司 | Early-strength polycarboxylate superplasticizer and preparation method and application thereof |
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| CN107739424A (en) * | 2017-11-07 | 2018-02-27 | 上海三瑞高分子材料股份有限公司 | A kind of solid protects the polycarboxylate water-reducer and preparation method thereof that collapses |
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| CN110642989B (en) * | 2018-06-26 | 2021-01-15 | 科之杰新材料集团有限公司 | Preparation method of micro-crosslinked powder polycarboxylate superplasticizer |
| CN108948261B (en) * | 2018-07-31 | 2019-11-01 | 四川大学 | High-strength heat-resistant fireproof concrete viscosity modifying agent and its preparation method and application |
| CN111793216A (en) * | 2020-07-06 | 2020-10-20 | 江苏奥莱特新材料股份有限公司 | Early-strength polycarboxylate water reducing agent and preparation method thereof |
| CN112708058B (en) * | 2020-11-03 | 2022-10-25 | 科之杰新材料集团有限公司 | Ether anticorrosion polycarboxylate superplasticizer and preparation method thereof |
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